Polycarbonate-polyorganosiloxane copolymer and method for producing same

Abstract

Provided is a polycarbonate-polyorganosiloxane copolymer, including a specific polycarbonate block unit (A) and a specific polyorganosiloxane block unit (B), in which in a differential molecular weight distribution curve obtained from measurement of the polyorganosiloxane block unit (B) by gel permeation chromatography using the polystyrene calibration curve, the curve having an axis of abscissa indicating a logarithmic value log(M) of a molecular weight M and an axis of ordinate indicating dw/d log(M) obtained by differentiating a concentration fraction w with respect to the logarithmic value log(M) of the molecular weight, (1) a dw/d log(M) value becomes maximum in a range of 3.4≦log(M)≦4.0, and (2) in the differential molecular weight distribution curve, a ratio of a value obtained by integrating the dw/d log(M) value over a range of 4.0≦Log(M)≦4.5 to a value obtained by integrating the dw/d log(M) value over the entire range of the log(M) is 6% or more and 40% or less.

The invention claimed is: 
     
       1. A polycarbonate-polyorganosiloxane copolymer, comprising:
 a polycarbonate block (A) comprising a repeating unit represented by the following general formula (I); and 
 a polyorganosiloxane block (B) comprising a repeating unit represented by the following general formula (II), 
 wherein in a differential molecular weight distribution curve obtained from measurement of the polyorganosiloxane block (B) by gel permeation chromatography using the polystyrene calibration curve, the curve having an axis of abscissa indicating a logarithmic value log(M) of a molecular weight M and an axis of ordinate indicating dw/d log(M) obtained by differentiating a concentration fraction w with respect to the logarithmic value log(M) of the molecular weight, 
 (1) a dw/d log(M) value becomes maximum in a range of 3.4≦log(M)≦4.0, and 
 (2) in the differential molecular weight distribution curve, a ratio of a value obtained by integrating the dw/d log(M) value over a range of 4.0≦log(M)≦4.5 to a value obtained by integrating the dw/d log(M) value over an entire range of the log(M) is 6% or more and 40% or less: 
 
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 2  each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, —S—, —SO—, —SO 2 —, —O—, or —CO—, R 3  and R 4  each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and a and b each independently represent an integer of 0 to 4. 
     
     
       2. The polycarbonate-polyorganosiloxane copolymer according to  claim 1 , wherein the polyorganosiloxane block (B) has an average chain length of 20 to 85. 
     
     
       3. The polycarbonate-polyorganosiloxane copolymer according to  claim 1 , wherein a content of the polyorganosiloxane block (B) is 0.5 mass % to 20.0 mass % of the polycarbonate-polyorganosiloxane copolymer. 
     
     
       4. The polycarbonate-polyorganosiloxane copolymer according to  claim 1 , wherein the polycarbonate-polyorganosiloxane copolymer has a viscosity-average molecular weight of 12,000 to 40,000. 
     
     
       5. The polycarbonate-polyorganosiloxane copolymer according to  claim 1 , wherein in the general formula (I), a and b each represent 0, and X represents a single bond or an alkylene group having 1 to 8 carbon atoms. 
     
     
       6. The polycarbonate-polyorganosiloxane copolymer according to  claim 1 , wherein in the general formula (I), a and b each represent 0, and X represents an alkylene group having 3 carbon atoms. 
     
     
       7. The polycarbonate-polyorganosiloxane copolymer according to  claim 1 , wherein in the general formula (II), R 3  and R 4  each represent a methyl group. 
     
     
       8. A molded article, which is obtained by molding the polycarbonate-polyorganosiloxane copolymer of  claim 1 . 
     
     
       9. A method of producing the polycarbonate-polyorganosiloxane copolymer of  claim 1 , comprising using a polyorganosiloxane represented by the following general formula (ii) or (iii) as a raw material: 
       
         
           
           
               
               
           
         
       
       wherein R 3  to R 6  each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, Y and Y′ each independently represent a single bond, or an organic residue comprising —C(═O)—, an aliphatic moiety, or an aromatic moiety, the organic residue being bonded to Si and O or to Si and Z, n represents an average number of repetitions, m represents 0 or 1, Z each independently represent a halogen, —R 7 OH, —R 7 COOH, —R 7 NH 2 , —R 7 NHR 8 , —COOH, or —SH, R 7  represents a linear, branched, or cyclic alkylene group, an aryl-substituted alkylene group, an aryl-substituted alkylene group that may have an alkoxy group on a ring thereof, an arylene group that may be substituted, or an arylene alkyl-substituted aryl group, R 8  represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, Z′ each independently represent —R 7 O—, —R 7 COO—, —R 7 NH—, —COO—, or —S—, R 7  represents a linear, branched, or cyclic alkylene group, an aryl-substituted alkylene group, an aryl-substituted alkylene group that may have an alkoxy group on a ring thereof, an arylene group that may be substituted, or an arylene alkyl-substituted aryl group, and β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid,
 the raw material polyorganosiloxane satisfying the following (1) and (2): 
 in a differential molecular weight distribution curve obtained from measurement of the polyorganosiloxane by gel permeation chromatography using the polystyrene calibration curve, the curve having an axis of abscissa indicating a logarithmic value log(M) of a molecular weight M and an axis of ordinate indicating dw/d log(M) obtained by differentiating a concentration fraction w with respect to the logarithmic value log(M) of the molecular weight, 
 (1) a dw/d log(M) value becomes maximum in a range of 3.4≦log(M)≦4.0, and 
 (2) in the differential molecular weight distribution curve, a ratio of a value obtained by integrating the dw/d log(M) value over a range of 4.0≦log(M)≦4.5 to a value obtained by integrating the dw/d log(M) value over an entire range of the log(M) is 6% or more and 40% or less. 
 
     
     
       10. The method of producing the polycarbonate-polyorganosiloxane copolymer according to  claim 9 , wherein in the general formula (ii) or (iii), an average chain length n is 20 to 85. 
     
     
       11. The method of producing the polycarbonate-polyorganosiloxane copolymer according to  claim 9 , wherein in the general formula (ii) or (iii), R 3  and R 4  each represent a methyl group. 
     
     
       12. A polyorganosiloxane, which is represented by the following general formula (ii) or (iii): 
       
         
           
           
               
               
           
         
       
       wherein R 3  to R 6  each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, Y and Y′ each independently represent a single bond, or an organic residue comprising —C(═O)—, an aliphatic moiety, or an aromatic moiety, the organic residue being bonded to Si and O or to Si and Z, n represents an average number of repetitions, m represents 0 or 1, Z each independently represent a halogen, —R 7 OH, —R 7 COOH, —R 7 NH 2 , —R 7 NHR 8 , —COOH, or —SH, R 7  represents a linear, branched, or cyclic alkylene group, an aryl-substituted alkylene group, an aryl-substituted alkylene group that may have an alkoxy group on a ring thereof, an arylene group that may be substituted, or an arylene alkyl-substituted aryl group, R 8  represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, Z′ each independently represent —R 7 O—, —R 7 COO—, —R 7 NH—, —COO—, or —S—, R 7  represents a linear, branched, or cyclic alkylene group, an aryl-substituted alkylene group, an aryl-substituted alkylene group that may have an alkoxy group on a ring thereof, an arylene group that may be substituted, or an arylene alkyl-substituted aryl group, and β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid,
 the polyorganosiloxane satisfying the following (1) and (2): 
 in a differential molecular weight distribution curve obtained from measurement of the polyorganosiloxane by gel permeation chromatography using the polystyrene calibration curve, the curve having an axis of abscissa indicating a logarithmic value log(M) of a molecular weight M and an axis of ordinate indicating dw/d log(M) obtained by differentiating a concentration fraction w with respect to the logarithmic value log(M) of the molecular weight, 
 (1) a dw/d log(M) value becomes maximum in a range of 3.4≦log(M)≦4.0, and 
 (2) in the differential molecular weight distribution curve, a ratio of a value obtained by integrating the dw/d log(M) value over a range of 4.0≦log(M)≦4.5 to a value obtained by integrating the dw/d log(M) value over an entire range of the log(M) is 6% or more and 40% or less. 
 
     
     
       13. The polyorganosiloxane according to  claim 12 , wherein in the general formula (ii) or (iii), an average chain length n is 20 to 85. 
     
     
       14. A polycarbonate-polyorganosiloxane copolymer comprising a polycarbonate block (A) comprising a repeating unit represented by the following general formula (I); and a polyorganosiloxane block (B) comprising a repeating unit represented by the following general formula (II), wherein the copolymer is obtained by using a polyorganosiloxane represented by the following general formula (ii) or (iii) as a raw material: 
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, —S—, —SO—, —SO 2 —, —O—, or —CO—, R 3  and R 4  each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and a and b each independently represent an integer of 0 to 4, 
       
       
         
           
           
               
               
           
         
       
       wherein R 3  to R 6  each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, Y and Y′ each independently represent a single bond, or an organic residue comprising —C(═O)—, an aliphatic moiety, or an aromatic moiety, the organic residue being bonded to Si and O or to Si and Z, n represents an average number of repetitions,
 m represents 0 or 1, 
 Z each independently represent a halogen, —R 7 OH, —R 7 COOH, —R 7 NH 2 , —R 7 NHR 8 , —COOH, or —SH, R 7  represents a linear, branched, or cyclic alkylene group, an aryl-substituted alkylene group, an aryl-substituted alkylene group that may have an alkoxy group on a ring thereof, an arylene group that may be substituted, or an arylene alkyl-substituted aryl group, R 8  represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, Z′ each independently represent —R 7 O—, —R 7 COO—, —R 7 NH—, —COO—, or —S—, R 7  represents a linear, branched, or cyclic alkylene group, an aryl-substituted alkylene group, an aryl-substituted alkylene group that may have an alkoxy group on a ring thereof, an arylene group that may be substituted, or an arylene alkyl-substituted aryl group, 
 
       and
 β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid, the raw material polyorganosiloxane satisfying the following (1) and (2): 
 in a differential molecular weight distribution curve obtained from measurement of the polyorganosiloxane by gel permeation chromatography using the polystyrene calibration curve, the curve having an axis of abscissa indicating a logarithmic value log(M) of a molecular weight M and an axis of ordinate indicating dw/d log(M) obtained by differentiating a concentration fraction w with respect to the logarithmic value log(M) of the molecular weight, 
 (1) a dw/d log(M) value becomes maximum in a range of 3.4≦log(M)≦4.0, and 
 (2) in the differential molecular weight distribution curve, a ratio of a value obtained by integrating the dw/d log(M) value over a range of 4.0≦log(M)≦4.5 to a value obtained by integrating the dw/d log(M) value over an entire range of the log(M) is 6% or more and 40% or less. 
 
     
     
       15. A method of producing the polycarbonate-polyorganosiloxane copolymer comprising: a polycarbonate block (A) comprising a repeating unit represented by the following general formula (I) and a polyorganosiloxane block (B) comprising a repeating unit represented by the following general formula (II), using a polyorganosiloxane represented by the following general formula (ii) or (iii) as a raw material; 
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, —S—, —SO—, —SO 2 —, —O—, or —CO—, R 3  and R 4  each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and a and b each independently represent an integer of 0 to 4, 
       
       
         
           
           
               
               
           
         
       
       wherein R 3  to R 6  each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, Y and Y′ each independently represent a single bond, or an organic residue comprising —C(═O)—, an aliphatic moiety, or an aromatic moiety, the organic residue being bonded to Si and O or to Si and Z, n represents an average number of repetitions, m represents 0 or 1, Z each independently represent a halogen, —R 7 OH, —R 7 COOH, —R 7 NH 2 , —R 7 NHR 8 , —COOH, or —SH, R 7  represents a linear, branched, or cyclic alkylene group, an aryl-substituted alkylene group, an aryl-substituted alkylene group that may have an alkoxy group on a ring thereof, an arylene group that may be substituted, or an arylene alkyl-substituted aryl group, R 8  represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, Z′ each independently represent —R 7 O—, —R 7 COO—, —R 7 NH—, —COO—, or —S—, R 7  represents a linear, branched, or cyclic alkylene group, an aryl-substituted alkylene group, an aryl-substituted alkylene group that may have an alkoxy group on a ring thereof, an arylene group that may be substituted, or an arylene alkyl-substituted aryl group, and β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid, the polyorganosiloxane satisfying the following (1) and (2):
 in a differential molecular weight distribution curve obtained from measurement of the polyorganosiloxane by gel permeation chromatography using the polystyrene calibration curve, the curve having an axis of abscissa indicating a logarithmic value log(M) of a molecular weight M and an axis of ordinate indicating dw/d log(M) obtained by differentiating a concentration fraction w with respect to the logarithmic value log(M) of the molecular weight, 
 (1) a dw/d log(M) value becomes maximum in a range of 3.4≦log(M)≦4.0, and 
 (2) in the differential molecular weight distribution curve, a ratio of a value obtained by integrating the dw/d log(M) value over a range of 4.0≦log(M)≦4.5 to a value obtained by integrating the dw/d log(M) value over an entire range of the log(M) is 6% or more and 40% or less.